Quasi-solid-state lithium metal batteries are considered as one of the most promising energy storage devices, and the application of ionic liquids (ILs) as a new generation of functionalized electrolyte components in lithium metal batteries has become one of the research focuses. In this review, the very recent research work related to using IL to develop quasi-solid-state electrolytes and their influences on the performances of quasi-solid-state lithium metal batteries were surveyed and summarized, suggesting that the introduction of ILs can improve the ionic conductivity, broaden the electrochemical stability window, and enhance the electrochemical stability of selected electrolytes. Moreover, using ILs to prepare high-performance electrodes with unique microstructures and uniform distribution of fillers were also introduced. The composite quasi-solid-state electrolytes were suggested as the mainstream of electrolytes in the future due to the combination of the advantages of inorganic and polymer quasi-solid-state electrolytes, and their development challenges in high energy and high safety quasi-solid-state lithium metal batteries were also discussed.

The Li dendrites introduced by the inhomogeneous Li-ion flux are the barriers to the commercialization of solid-state lithium metal batteries (LMBs). Increasing the Li⁺ transference number and homogenizing the Li⁺ flux are two effective strategies to solve the aforementioned issues. Herein, a flexible composite solid electrolyte (CSE) with an enhanced Li⁺ transference number, high ionic conductivity, and self-healing function was synthesized via a simple template method. Boron nitride (BN) nanosheets with high specific surface area and richly porous structure were used as the passive inorganic filler, homogenizing the Li⁺ flux and facilitating the Li⁺ transmission. The flexible and self-healing features of the CSE reduced the interface resistance and considerably prolonged their cycling life. By exploiting stress–strain curves before and after healing, along with physical characterizations, the self-healing efficiency was obtained and the dendrite suppress mechanisms at the electrode/CSE interface were discussed. Finally, the assembled LiFePO₄/Li cell with optimized CSE exhibited impressive cycling performance and delivered a steady discharge capacity up to 152 mA h g⁻¹ after 300 cycles at 0.1C. This universal strategy can be used in other emerging energy storage fields to boost high energy density and long cycling life.

LiF-rich solid-electrolyte-interphase (SEI) can suppress the formation of lithium dendrites and promote the reversible operation of lithium metal batteries. Regulating the composition of naturally formed SEI is an effective strategy, while understanding the impact and role of fluorine (F)-based Li-salts on the SEI characteristics is unavailable. Herein, LiFSI, LiTFSI, and LiPFSI are selected to prepare solid polymer electrolytes (SPEs) with poly(ethylene oxide) and polyimide, investigating the effects of molecular size, F contents and chemical structures (F-connecting bonds) of Li-salts and revealing the formation of LiF in the SEI. It is shown that the F-connecting bond is more significant than the molecular size and F element contents, and thus the performances of cells using LiPFSI are slightly better than LiTFSI and much better than LiFSI. The SPE containing LiPFSI can generate a high amount of LiF, and SPEs containing LiPFSI and LiTFSI can generate Li3N, while there is no Li3N production in the SEI for the SPE containing LiFSI. The preferential breakage bonds in LiPFSI are related to its position to Li anode, where Li-metal as the anode is important in forming LiF, and consequently the LiPFSI reduction mechanism is proposed. This study will boost other energy storage systems beyond Li-ion chemistries.

Multilayer composite solid electrolytes (CSEs) exhibit many advantages over uniform monolayer CSEs but are hindered by high interlayer resistance and complex preparation methods. Herein, for the first time, a natural sedimentation strategy was developed to construct concentration gradient CSEs (GCSEs) for lithium-metal batteries (LMBs). This method utilizes intrinsic gravity and photopolymerization to achieve multiple functions in the monolayer, avoiding additional interlayer resistance and reducing preparation time. Owning to the concentration gradient structure, the Li+ transport on the PolyIL-rich side relies on the weak solvation of Li+ with EMIMTFSI, while the Li+ transport on the LLZTO-rich side follows the 'vehicular diffusion' mechanism with the aid of TFSI−, improving the Li+ transport and enhances the Li+ transference number, leading to the high stability to 2300 h for the Li//Li cell and stable operation at 4.3 V with 89.6 % capacity retention after 100 cycles for the assembled LMB. Moreover, compared with the monolayer uniform hybrid CSEs, the gradient structure alleviates uncoordinated thermal expansion between LLZTO and PolyIL, avoiding stress increase during cycling and battery capacity fade. This gradient strategy mitigates high interlayer resistance and offers a universal path to address the sluggish Li+ transportation in multilayer CSEs and improves compatibility between the electrolyte and electrodes in fabricating solid-state batteries.